CN102731262A - Method for recovering phenolic compounds from coal-derived oil products - Google Patents
Method for recovering phenolic compounds from coal-derived oil products Download PDFInfo
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Abstract
The invention relates to a method for recovering phenolic compounds from coal-derived oil products by using a substance containing calcium oxide or calcium hydrate. The method is characterized by comprising the following steps: 1) mixing the substance containing calcium oxide or calcium hydrate with a coal-derived oil product and allowing the substance to react with the oil product to produce phenol calcium salt; 2) separating the phenol calcium salt from the dephenolized oil product and allowing gas containing carbon dioxide to enter into a solution of the phenol calcium salt; 3) allowing a crude phenol liquid layer and light calcium carbonate solid to be precipitated through the reaction between carbon dioxide and the phenol calcium salt; and 4) recovering layered crude phenol liquid and separating the by-product of light calcium carbonate through filtration and dehydration. The substance containing calcium oxide or calcium hydrate can be quicklime, slaked lime, the chemical of calcium oxide, the chemical of calcium hydrate or a mixture of the above-mentioned components. The coal oil product can be coal tar or fraction thereof, or direct coal liquefaction effluent or fraction thereof.
Description
Technical field
The present invention relates to material that a kind of utilization contains quicklime or calcium hydroxide reclaims phenolic cpd from coal-based oil product method, particularly a kind of method that from coal tar or coal direct liquefaction oil, reclaims phenolic cpd.
Background technology
Coal tar derives from the product liquid that obtains in the coal destructive distillation, wherein contains a large amount of phenolic cpds.Coal direct liquefaction oil is made by the coal hydrogenation liquefaction, wherein also contains a large amount of phenolic cpds.Phenolic cpd is a kind of very deleterious material for the burning utilization of oil product, and it can cause problems such as the increase of oil product carbon residue amount, oil product variable color and corrodibility.If tar is carried out unifining, containing oxygen class functional group and can increase hydrogen consumption in the phenolic cpd, and influence the stability of oil product.Simultaneously, phenolic cpd is again an important chemical material, at aspects such as synthon, engineering plastics, agricultural chemicals, medicine and dyestuff intermediates purposes is widely arranged.From coal tar, extract phenolic cpd, both helped guaranteeing the quality of hydrogenation oil product, can obtain the chemical of high added value again.
Along with the semicoke industrial expansion is produced in coal processing inferior such as China's brown coal, the output that contains phenol tar presents the form of cumulative year after year.Reclaim after taking inexpensive method that the phenolic cpd in the oil product is removed; Not only can reduce the hydrogen consumption of follow-up hydrogenation process; Improve the economic value added of tar products; Can also expand the utilize approach of coal-based oil product, have very important significance for the upgrading of the novel industry of China's Coal Chemical Industry and the lifting of profit as non-fuel oil.
The method that in industry, phenolic cpd is removed from oil product at present is mainly sodium hydroxide alkali cleaning method, also has yellow soda ash or phenol sodium solution extraction process, alcohol solution extraction process in addition, precipitation by metallic ion method etc., but all can't replace sodium hydroxide alkali cleaning method.Phenolic cpd has slightly acidic, uses sodium hydroxide solution can phenol be transferred to from oil in the aqueous solution, separates with neutral oil.Have simple to operate, the characteristics that separation efficiency is high.But the cost recovery that the higher price of sodium hydroxide has improved phenolic cpd has limited its large-scale promotion and application.
Contain a large amount of quicklime or calcium hydroxide in the lime; The major ingredient of unslaked lime is a quicklime; The major ingredient of white lime is a calcium hydroxide; All can generate the phenol calcium salt and separate, can reclaim crude phenols and generate the by product light calcium carbonate after in the phenol calcium salt, feeding the gas contain carbonic acid gas with coal-based oil product with phenolic cpd.Lime is a kind of material of construction widely, compares with sodium hydroxide to have tangible price advantage.Lime method and yellow soda ash or phenol sodium solution extraction process, alcohol solution extraction process, precipitation by metallic ion method are compared also has huge cost advantage.
According to the data of patent and Literature Consult, having no a kind of is to utilize quicklime or calcium hydroxide from coal-based oil product, to reclaim the technology of phenolic cpd.Than the recovery method of other phenolic cpds, quicklime or calcium hydroxide derive from lime, and price is very cheap, have huge cost advantage.
Prior art mainly contains following several kinds:
Prior art one:
Patent 200910197912.1 discloses a kind of coal tar crude phenol working method and device; Said method is mixed the sulfuric acid of clean phenates with concentration 40%-98%; Low speed gets into mixing tank; Reaction generates the mixed solution of phenates, crude phenols and sodium sulfate, makes phenates, crude phenols and sodium sulfate mixed solution get into first reactor reaction at a high speed then, and reacted material gets into second reactor drum through injector; The come out mixed solution of crude phenols and sodium sulfate of liquid phase, mixed solution is isolated crude phenols and sodium sulfate waste water at last in separator.
Prior art two:
Patent 200910195020.8 discloses treatment of waste gas method in a kind of producing crude phenol from coal tar process; Be in coal tar processing crude phenols process; Utilization contains the phenol cut and the clean sodium phenates of intermediate product that generates by what NaOH solution washing coal tar distillation obtained, in the absorption tower, absorbs to produce and decomposes the waste gas that contains acid mist in the clean sodium phenolate process from sulfuric acid process.
Prior art three:
Patent 200910116884.6 discloses a kind of high density petroleum phenol that reclaims in petrochemical refining's gasoline alkaline residue, obtains the method for high quality refined phenol series product.Alkaline residue is handled through compound complex agent; Crude phenols are isolated in acidifying again, and crude phenols are carried out rectification under vacuum, obtain mixed phenol; Adding activated carbon of sorbent adsorbs; Filter through pressure filter then, the mixed phenol after the separation gets into and carries out rectification under vacuum in the rectifying tower, obtains the petroleum phenol that total sulfur content is lower than 60ppm.
Prior art four:
Patent 200910049826.6 discloses a kind of utilization and has contained phenol tar and prepare gac, and reclaims the wherein method of high added value phenol products simultaneously.Join in the charring furnace through containing phenol tar; Carry out gas purging when heating up; Charing can obtain gac after finishing, and the Resorcinol product utilization solvent in the tail gas cools off and reclaims, and the separation and purification system that returns phenol hydroxylation technology accomplishes the Resorcinol product and reclaims.
Prior art five:
Patent 200810015302.0 discloses a kind of diesel alkaline residue and has strengthened the method for taking off neutral oil and step reclamation of naphthenic acids and phenol; It may further comprise the steps: controlled temperature is at 50-100 ℃; Diesel alkaline residue combines breakdown of emulsion with high-efficiency polymerization type emulsion splitter, saltcake, sulfuric acid and heating power method, and emulsion splitter, saltcake consumption are respectively alkaline residue heavy 0.003%-0.03%, 10%-80%, and the sulfuric acid control pH value that adds 1mol/L is at 6-10; Leave standstill breakdown of emulsion layering after 0.5-6 hour, tell alkali waste water and diesel oil.The sulfuric acid acidation that alkali waste water adds 1mol/L stirs, and controlled temperature is at 50-80 ℃, and the pH value left standstill 1-8 hour at 4-6, and Separation and Recovery phenol is acidified to pH value 2-4 again, leaves standstill the Separation and Recovery naphthenic acid 1-8 hour.
Prior art six:
Patent 200810014997.0 discloses the method for a kind of diesel alkaline residue step reclamation of naphthenic acids and phenol, has solved that the traditional technology raw material availability is low, the not high deficiency of product purity, a kind of energy-efficient method is provided, and has produced highly purified product.It may further comprise the steps: remove the sulfuric acid acidation that alkaline sewage behind the neutral oil adds 1mol/L and stir, controlled temperature is at 50-80 ℃, and control pH value is at 4-6; Left standstill 1-8 hour, Separation and Recovery phenol is acidified to pH value 2-4 again; Left standstill the Separation and Recovery naphthenic acid 1-8 hour.
Prior art seven:
Patent 200610107947.8 discloses a kind of method prepare Viteolin of from cottonseed oil deodorizer distillate, separating, and fresh cottonseed oil deodorizer distillate after through material composition mensuration and the methyl alcohol proportional mixing, is carried out esterification under certain condition.After reaction finishes, be that raw material carries out transesterification reaction with the ester layer, cooling, suction filtration.Set suitable parameters, the liquid concentrator of raw material carried out short-path distillation, the Viteolin liquid concentrator.In the method, the short-path distillation mild condition, natural tocopherol is on the basis of not losing basically, and single flash purity can reach more than 60%.
Prior art eight:
Patent 01818649.1 discloses a kind of method from bis-phenol tar recovery useful component, passes through to spray fluidizing BPA tar heating recovery phenol and isopropenyl phenol in the presence of a kind of basic catalyst simultaneously from BPA tar.Spraying conspicuously increases the efficient of phenol and isopropenyl phenol recovery.The isopropenyl phenol that reclaims can change bis-phenol 4 into through being reflected at phenol and a kind of an acidic catalyst in the overhead product.
Prior art nine:
Patent 201010576069.0 discloses a kind of making method of biomass coke tar industry creosote, comprising: step 1, raw material are collected and anhydrous biomass coke tar are carried out air distillation, the cut of biomass collection tar in 190～230 ℃ of processes; Step 2, alkali cleaning deacidification; Step 3, separation neutral oil obtain industrial creosote.
Prior art ten:
Patent 201110262946.1 discloses the preparation method of oily dephenolize extraction agent in a kind of tar from lignite, and it is refining refining with pickling that this method is carried out alkali cleaning with NaOH solution and sulfuric acid to oil in the tar from lignite successively, oil during generation is refining; Then; With ammonia soln to pickling after acid sludge carry out decomposition, isolate big and heavy pyridine liquid, big and heavy pyridine liquid obtains pyridine base through distillation; At last the pyridine base cut is added in the refining middle oil in proportion, promptly obtain oily dephenolize extraction agent in the tar from lignite.
Prior art 11:
Patent 201110102049.4 discloses a kind of method of from liquefied coal coil or coal tar, extracting phenolic cpd.May further comprise the steps: 1) liquefied coal coil or coal tar are handled in distillation, cut＜260 ℃ cut; 2) extraction agent is mixed the back layering with above-mentioned carbolic oil cut section; 3) separation and collection contain the extraction agent layer of phenolic cpd; 4) phenolic cpd in the extraction agent layer is carried out multistage back extraction and extract, obtain reverse-extraction agent-phenol solution and extraction agent; 5), reclaim reverse-extraction agent, recycle, and separation obtains crude phenols through the above-mentioned reverse-extraction agent-phenol solution of rectifying separation; 6) water vapour is carried and is removed the neutral oil of carrying secretly in the phenolic cpd, finally obtains the crude phenols product.
Prior art 12:
It is a kind of 3 that patent 200610026192.9 discloses, and the extraction process for purification of 5-xylenol extracts 3 of content >=80% with the crude phenols in the coal tar through rectifying; 5-xylenol cut; Be that raw material carries out fractional crystallization with this cut again, concrete steps are: a. is with 3 of content >=80%, and the heating of 5-xylenol cut makes it to be in a liquid state; Metering also drops in the mold constant temperature 0.5～2 hour; B. according to the operation of lowering the temperature stage by stage of 0.5～5 ℃/hr rate of temperature fall, slowly cool to no crystallisate constant temperature 0.5～2 hour when separating out; C. carry out warming temperature stage by stage according to 0.5～5 ℃/hr heating curve, the cutting cut obtains 3 of front-end volatiles, middle runnings and final cut content >=98%, 5-xylenol.
Prior art 13:
Patent 200610072928.6 discloses a kind of phenol, neighbour/Resorcinol and tar separation of water solution purifying plant and separating and purifying method thereof; It may further comprise the steps: liquid stock is fed dehydration distillation tower, the first dephenolize distillation tower, the second dephenolize distillation tower, decoking distillation tower successively, steams still, product rectifying tower deeply, through at the bottom of the cat head of said product distillation tower and tower, discharging pyrocatechol and Resorcinol respectively after the rectifying separation.
Prior art 14:
Patent 200610047787.2 disclose a kind of from contain phenol raw oil the method for separating phenols compounds.Contain the phenol raw material under certain condition, react with the saturated ammonia aqueous solution, during phenol and ammonia formation ammonium salt are soluble in the aqueous phase, from raw oil, phenol is deviate from, liquid is divided into two-layer, and oil phase and water are separated.Directly feed in the ammonium salt aqueous solution with carbonic acid gas then, carbonic acid gas and ammonium salt react the formation ammonium hydrogencarbonate, and the crude phenols that dissociate.
Prior art 15:
Patent 01110264.0 discloses a kind of method that from the dihydroxy-benzene mixture, removes phenol tar; It is characterized in that the resorcinol mixture; Especially contain and add the 3rd component in the mixture of Resorcinol (or Resorcinol) and phenol tar; Realize two phenol mixtures through underpressure distillation, especially the purpose of Resorcinol (or Resorcinol) and phenol tar separation.
Prior art 16:
Patent 02114790.6 discloses a kind of method of refining oil the alkaline waste water dephenolize, as the work in-process gasoline of extraction phase with adjusted the pH value and reclaimed naphthenic acid, crude phenols, Na
2CO
3Deng containing the phenol alkaline waste water behind the product,, leave standstill thereafter through mixer mixing with certain proportion, treat layering after, isolate work in-process gasoline, thereby remove the phenol in the alkaline waste water.
Prior art 17:
Patent 97121103.5 discloses a kind of recovery method of bis-phenol tar of synthetic ammonia phenyl phenylor paraffinic feed; Relate to the method for the valuable by product of the condensation course that reclaims phenol and ketone in the mother liquor that for example crystallisation process of 1: 1 affixture of phenol and bis-phenol obtains certainly, this mother liquor comprises the by-product impurities and the acidic impurities of the condensation reaction of phenol, bis-phenol, isomer, phenol and said ketone.With said mother liquor distillation/evaporation, so that stay the tar residue, it is as the raw material of the inventive method.
Prior art 18:
Patent 98110270.0 discloses the method for micro-phenol in a kind of quickly extracting and determining oil, mainly is to use Sep-pakNH
2Pillar is handled oil sample, the aldehydes matter wash-out that adsorbs on the coupled columns then, and elutriant carries out qualitative and quantitative analysis.This qualitative and quantitative analysis adopts the HPLC analytical method.
Prior art 19:
Patent 93104371.9 discloses a kind of method of from the phenol tar by product of producing the phenol process with isopropyl benzene, extracting phenol, comprising: a) preparation amine aqueous solution, b) phenol tar contacts with amine aqueous solution in the aqueous solution, to generate amino-phenol.C) the heating amino-phenol makes amino-phenol be decomposed into amine and phenol.
Prior art 20:
Patent 9312006.7 discloses the method for a kind of tar and waste water associating dephenolize, is the water source with the high-concentration phenolic wastewater, and the adding bases is mixed with 5～30% basic soln; As dephenolizer, tar is carried out dephenolize with this solution, in the tar dephenolize; Phenolic cpd in the waste water is removed in the lump; When improving high value phenols productive rate, the content of pollutents such as phenols in the waste water, oil, prussiate, Ammonia is all reduced greatly, whole technological process does not produce new phenolic wastewater.
Prior art 21:
Patent 96122012 discloses a kind of treatment process of phenol tar, and control condition is carried out phenol tar thermo-cracking under polyphosphoric acid is participated in, and reclaims value product.Can choose wantonly with dihydroxyphenyl propane tar with this understanding with the tar mixed pyrolysis, promote product yield.
Prior art 22
Coal journal the 10th phase of nineteen ninety-five " precipitator method reclaim the research of phenols in coal tar and the phenolic wastewater " is utilized the method for phenolic cpd in barium ion precipitate and separate coal tar and the phenolic wastewater; The salt and the phenolic cpd that contain barium ion through interpolation form deposition; Separate with waste water with tar, thereby reclaim phenolic cpd.
Prior art 23
Utilize the sodium hydroxide alkali cleaning from coal tar, to isolate phenolic cpd in 2009 34 10 phases of volume of coal journal " the phenol process study is proposed in the alkali cleaning of coal direct liquefaction product oil ", improved the added value that coal direct liquefaction oil utilizes.
Above prior art is technological different with the application all.
It is to adopt quicklime or calcium hydroxide as dephenolizer that prior art does not have a kind of, from coal-based oil product, reclaims the method for phenolic cpd.
Patented technology one, patented technology five, patented technology six need to add sulfuric acid and come souring soln to reclaim phenol, compare with quicklime or calcium hydroxide not have cost advantage.Patented technology two purposes are to use from sulfuric acid process decomposes the waste gas that contains acid mist in the clean sodium phenolate process, irrelevant with quicklime or calcium hydroxide dephenolize.Patented technology three, patented technology 12, patented technology 13, patented technology 15 main utilization distillatory physical methods reclaim phenolic cpd, and quicklime or calcium hydroxide and phenolic cpd reaction are chemical processes.Patented technology four, patented technology eight, patented technology 21 adopt charing, heating or cracked method to reclaim phenolic cpd, can cause precious phenolic cpd pyrolysis.Patented technology ten, patented technology 14, patented technology 19 adopt materials such as Ammonia, organic amine or pyridine from tar, to reclaim phenol, compare the cost free advantage with adopting quicklime or calcium hydroxide as dephenolizer.The material of patented technology ten, patented technology 20, technical literature 23 separating phenols is mainly sodium hydroxide, Pottasium Hydroxide, Marinco H and amine etc., and compares the cost free advantage with adopting quicklime or calcium hydroxide as dephenolizer.Patented technology five is for reclaiming phenol from diesel alkaline residue; Patented technology seven is for reclaiming phenol from Oleum Gossypii semen; Patented technology nine reclaims phenol for from biomass coke tar, reclaiming phenol in the patented technology 16 oil refining alkaline waste waters, all from coal-based oil product, reclaims phenol with employing quicklime or calcium hydroxide and has nothing to do.Patented technology 12, patented technology 17 employing crystalline methods reclaim phenol, and technical literature 22 adopts the sedimentary method of barium ions to reclaim phenol, from coal-based oil product, reclaims phenol with employing quicklime or calcium hydroxide and has nothing to do.Patented technology 18 relates to a kind of measuring method of phenol, and employing contains amino pillar and adsorbs, and is mainly used in the high-efficient liquid phase color spectrometry.
The major ingredient of unslaked lime is a quicklime, and the major ingredient of white lime is a calcium hydroxide, all can form the phenol calcium salt with the phenolic cpd in the coal-based oil product.
Unslaked lime and white lime are cheap, and the separation that is used for coal-based oil product phenolic cpd will have huge advantage.Employing contains the material of quicklime or calcium hydroxide as dephenolizer, through with coal-based oil product in phenolic cpd reaction form the phenol calcium salt, the phenol calcium salt is separated with the dephenolize oil product.Feed the gas that contains carbonic acid gas at the phenol calcium salt soln, separate out crude phenols layer and light calcium carbonate solid,, again by product light calcium carbonate filter dehydration is separated stratified crude phenols liquids recovery.Crude phenols can not only be reclaimed, the by product light calcium carbonate can also be obtained, and the ability absorbing carbon dioxide, emission of carbon-dioxide reduced.
The known product of being pulverized after milling by natural limestone is a water-ground limestone, and (1.1mL/g-1.4mL/g) is less for settling volume, so be called as water-ground limestone.The lime carbonate that is generated by the solution of calcium ions and carbon dioxide reaction is light calcium carbonate, and (2.4mL/g-2.8mL/g) is bigger for settling volume, so be called light calcium carbonate.Light calcium carbonate can be used as industries such as rubber, plastics, papermaking, coating and printing ink, is worth higher.
Summary of the invention
Employing contains the material of quicklime or calcium hydroxide as dephenolizer separating phenols compounds from coal-based oil product, can reduce coal-based oil manufacture cost effectively, and can produce the by product light calcium carbonate and reduce Carbon emission.
The present invention relates to a kind of method that from coal-based oil product, reclaims phenolic cpd with the material that contains quicklime or calcium hydroxide.It is characterized in that, comprise following steps: the material and the coal-based oil product hybrid reaction that 1) will contain quicklime or calcium hydroxide generate the phenol calcium salt; 2) the phenol calcium salt is separated with the dephenolize oil product, feed the gas that contains carbonic acid gas and get into the phenol calcium salt soln; 3) through the reaction of carbonic acid gas and phenol calcium salt, separate out crude phenols liquid level and light calcium carbonate solid; 4), again by product light calcium carbonate filter dehydration is separated with stratified crude phenols liquids recovery.
The described material that contains quicklime or calcium hydroxide comprises unslaked lime, white lime, quicklime chemical, calcium hydroxide chemical and their mixture.
Described coal-based oil product comprises coal tar or its cut, coal direct liquefaction oil or its cut.
The described gas that contains carbonic acid gas comprises the flue tail gas in fuel-burning power plant; The flue tail gas of coal firing boiler; The carbonated gas that produces after the water-gas shift in the coal gasification processes decomposes the dioxide gas that produces, pure carbonic acid gas industrial gasses in the limestone kiln.
Preferably; To contain the material of quicklime or calcium hydroxide and the step of coal-based oil product reaction generation phenol calcium salt is: will contain the material of quicklime or calcium hydroxide and the calcium hydroxide emulsion that water is made into 0.05-50%; Mix reaction with coal-based oil product, form dephenolize oil product layer and phenol calcium salt soln layer.
Preferably, with stratified crude phenols liquids recovery with by product light calcium carbonate filter dehydration and separating step is: will early stage and the carbonic acid gas solution left standstill layering of fully reacting, reclaim the crude phenols layer, again through filtering mode separation of lighter lime carbonate solid.
Preferably, contain dioxide gas in feeding and separate out in the light calcium carbonate solid process, adding sodium soap may command light calcium carbonate solid particulate is more tiny in solution, improves the light calcium carbonate quality.
The known product of being pulverized after milling by natural limestone is a water-ground limestone, and (1.1mL/g-1.4mL/g) is less for settling volume, so be called as water-ground limestone.The lime carbonate that is generated by the solution of calcium ions and carbon dioxide reaction is light calcium carbonate, and (2.4mL/g-2.8mL/g) is bigger for settling volume, so be called light calcium carbonate.Light calcium carbonate can be used as industries such as rubber, plastics, papermaking, coating and printing ink, is worth higher.
Meliority of the present invention is:
1. this method adopts the cheap material that contains quicklime or calcium hydroxide as dephenolizer, has reduced the industrial cost that from coal-based oil product, reclaims phenolic cpd of going up.
2. this method adopts the method that feeding contains dioxide gas from the phenol calcium salt, to separate out crude phenols and light calcium carbonate, has obtained valuable by product light calcium carbonate.
3. this method ability absorbing carbon dioxide reduces the discharging of carbonic acid gas to environment.
Description of drawings
Fig. 1 is the synoptic diagram of [specific embodiments 1]
Embodiment
[specific embodiments 1]
Serialization removes the mode of phenolic cpd in the coal tar:
The first step imports coal tar in the separation column through transfer pump, obtains to contain the coal-based oil product that phenol is comparatively concentrated through fractionation.
Second step added ball mill with lime, was crushed to the powder below 60 orders, and lime powder and water are stirred the emulsion of processing limy 10%.
The 3rd step progressively pumped into lime emulsion in the dephenolize tower according to the mode of Fig. 1, added the coal-based oil product that contains phenol simultaneously, the thorough mixing reaction, and the reacted phenol calcium aqueous solution is derived by the bottom.
In the 4th step, according to the mode of Fig. 1 the phenol calcium solution is pumped into and to analyse in the phenol tower.
The 5th step fed the carbonated flue gas according to the mode of Fig. 1 and is analysed in the phenol tower by the bottom input, treated the abundant postcooling layering of phenol calcium solution and carbon dioxide reaction.
The 6th step, derive crude phenols liquid by analysing the phenol top of tower, reclaim storage.
The 7th step, will analyse phenol tower bottom light calcium carbonate solid filtering and separate, make light calcium carbonate product through deslimer dehydration after drying.
The implementation result explanation: this embodiment is the serialization production of lime dephenolizing process, and raw material is lime and carbonic acid gas flue gas, and product is dephenolize oil product, crude phenols liquid, light calcium carbonate.1 ton of lime of every consumption, about 3.3 tons of recyclable crude phenols liquid, and produce 1.7 tons of by product light calcium carbonates.After the lime dephenolize, the phenol amount that contains in the coal-based oil product is reduced to below 0.5%, and most phenolic cpds all are recovered, and dephenolize efficient is higher.
[specific embodiments 2]
The intermittent mode that removes phenolic cpd in the carbolic oil:
The first step is pulverized the container that has stirrer that the back adds 100L with lime 3kg, adds 50L water, starts stirrer liming is stirred well to emulsus.
In second step, adding phenol content is 20% carbolic oil 50L, and encloses container stirred 1 hour.
The 3rd step, static to dephenolize oil and the layering of phenol calcium saline solution, the phenol calcium saline solution is derived.
The 4th step, collect enough phenol calcium saline solutions, with transport trolley the phenol calcium saline solution is transported near the coal-burning power plant.
The 5th step, the phenol calcium saline solution import diameter be 2m highly in the dephenolize tower of 20m, feed the flue tail gas 2 hours in the fuel-burning power plant of containing carbonic acid gas, treat solution cooling layering.
The 6th step, derive crude phenols liquid by analysing the phenol top of tower, will analyse phenol tower bottom light calcium carbonate solid filtering and separate, make light calcium carbonate product through deslimer dehydration after drying.
The implementation result explanation: the treatment capacity of intermittent dephenolizing process is less, but intermittent dephenolizing process cost of investment is little, can be with handling near the source of the gas that concentrates on flue gas after the collection of phenol calcium saline solution.The dephenolize efficient and the serialization difference of intermittent dephenolizing process are little, containing the phenol amount and also can be reduced to below 0.5% in the coal-based oil product.Compare with the serialization dephenolizing process and to be limited by the production capacity smaller defect.
[specific embodiments 3]
Another kind of intermittent dephenolize mode:
The first step is pulverized back adding 60L with 4kg white lime and is had in the container of well heater.
In second step, adding phenol content is 20% carbolic oil 50L, opens well heater, Heating temperature to 150 ℃ stirring.
In the 3rd step, question response after 1 hour filters out the phenol calcium salt, and oil strain is a dephenolize oil.
The 4th step, collect enough phenol calcium salts after, with transport trolley the phenol calcium saline solution is transported near the coal-burning power plant.
The 5th step was mixed with the aqueous solution with the phenol calcium salt, imported diameter and be 2m highly in the dephenolize tower of 20m, fed the flue tail gas 2 hours in the fuel-burning power plant of containing carbonic acid gas, treated solution cooling layering.
The 6th step, derive crude phenols liquid by analysing the phenol top of tower, will analyse phenol tower bottom light calcium carbonate solid filtering and separate, make light calcium carbonate product through deslimer dehydration after drying.
The implementation result explanation: this intermittent dephenolize mode is in the dephenolize process and do not rely on the aqueous solution, but needs heating to make calcium hydroxide and phenolic cpd reaction in the white lime form the phenol calcium salt.Handle 20% carbolic oil 50L fully and need consume white lime 4kg, cost is high slightly, and on the other hand, heating also can increase energy consumption, consumed energy in the dephenolize process.
Claims (6)
1. the utilization material that contains quicklime or calcium hydroxide reclaims the method for phenolic cpd from coal-based oil product, it is characterized in that comprise following steps: the material and the coal-based oil product hybrid reaction that 1) will contain quicklime or calcium hydroxide generate the phenol calcium salt; 2) the phenol calcium salt is separated with the dephenolize oil product, feed the gas that contains carbonic acid gas and get into the phenol calcium salt soln; 3) through the reaction of carbonic acid gas and phenol calcium salt, separate out crude phenols liquid level and light calcium carbonate solid; 4), again by product light calcium carbonate filter dehydration is separated with stratified crude phenols liquids recovery.
2. method according to claim 1, the wherein said material that contains quicklime or calcium hydroxide comprises unslaked lime, white lime, quicklime chemical, calcium hydroxide chemical and their mixture.
3. method according to claim 1, wherein said coal-based oil product comprises coal tar or its cut, coal direct liquefaction oil or its cut.
4. method according to claim 1; The gas that contains carbonic acid gas described in the step comprises the flue tail gas in fuel-burning power plant; The flue tail gas of coal firing boiler; The carbonated gas that produces after the water-gas shift in the coal gasification processes decomposes the dioxide gas that produces, pure carbonic acid gas industrial gasses in the limestone kiln.
5. method according to claim 1; According to following mode performing step 1) in will contain quicklime or calcium hydroxide the reaction of material and coal-based oil product generate the step of phenol calcium salt: will contain the material of quicklime or calcium hydroxide and the calcium hydroxide emulsion that water is made into 0.05-50%; Mix reaction with coal-based oil product, form dephenolize oil product layer and phenol calcium salt soln layer.
6. method according to claim 1; According to following mode performing step 4) with stratified crude phenols liquids recovery with by product light calcium carbonate filter dehydration is separated: will early stage and the carbonic acid gas solution left standstill layering of fully reacting; Reclaim the crude phenols layer, again through filtering mode separation of lighter lime carbonate solid.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103965950A (en) * | 2014-04-29 | 2014-08-06 | 神华集团有限责任公司 | Method for separating phenols in coal liquefaction oil |
| CN104845662A (en) * | 2015-04-24 | 2015-08-19 | 神华集团有限责任公司 | A method for extracting phenolic compounds in coal liquefaction oil |
| CN110330408A (en) * | 2019-07-23 | 2019-10-15 | 山西永东化工股份有限公司 | A kind of gas Cycle-decomposition coking crude phenol coproduction light calcium production method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103965950A (en) * | 2014-04-29 | 2014-08-06 | 神华集团有限责任公司 | Method for separating phenols in coal liquefaction oil |
| CN103965950B (en) * | 2014-04-29 | 2015-07-15 | 神华集团有限责任公司 | Method for separating phenols in coal liquefaction oil |
| CN104845662A (en) * | 2015-04-24 | 2015-08-19 | 神华集团有限责任公司 | A method for extracting phenolic compounds in coal liquefaction oil |
| CN110330408A (en) * | 2019-07-23 | 2019-10-15 | 山西永东化工股份有限公司 | A kind of gas Cycle-decomposition coking crude phenol coproduction light calcium production method |
| CN111892484A (en) * | 2020-05-27 | 2020-11-06 | 河北诚江医药科技有限公司 | Continuous decolorizing and deodorizing method for low-temperature crude phenol in coal gasification |
| CN111892484B (en) * | 2020-05-27 | 2023-06-20 | 河北正华科技有限公司 | Continuous decoloring and deodorizing method for low-temperature crude phenol in coal gasification |
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